US6846491B1 - Clear, polymeric gel composition and method for producing the same - Google Patents
Clear, polymeric gel composition and method for producing the same Download PDFInfo
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- US6846491B1 US6846491B1 US10/040,412 US4041202A US6846491B1 US 6846491 B1 US6846491 B1 US 6846491B1 US 4041202 A US4041202 A US 4041202A US 6846491 B1 US6846491 B1 US 6846491B1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/068—Microemulsions
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8164—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q13/00—Formulations or additives for perfume preparations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
Definitions
- This invention relates to the chemical arts.
- it relates to a polymeric gel composition and a method for producing the same.
- Hydrophilic polymer compositions have been described in U.S. Pat. Nos. 5,334,691 and 4,362,841.
- the gels have been shown to contain between 0.1-70 wt. % water. It is a drawback of these gels that when hydrophobic liquids, such as perfumes, insecticides, and insect repellants, are added, the gels are not clear, but are opaque, translucent, or heterogeneous.
- the gel composition is the reaction product of a microemulsion containing (a) from 1-70 wt. %, preferably from 140 wt. %, and more preferably from 10-25 wt. % of an anhydride functionalized polymer, (b) from 0.1-40 wt. %, preferably from 0.1-20 wt. %, and most preferably from 0.5-5 wt. % of a cross-linking agent, (c) from 0.01-50 wt. %, preferably from 0.1-20 wt. %, and more preferably from 0.5-10 wt.
- % surfactant (d) from 0.01-30 wt. %, preferably from 0.1-10 wt. %, and more preferably from 0.1-5 wt. % water, and (e) from 10.0-95.0 wt. % of a hydrophobic liquid, based on the total weight of the polymeric gel composition.
- the combined proportion of (d) and (e) equals at least 30 wt. %, based on the total weight of the polymeric gel composition.
- Representative anhydride functionalized polymers include maleinized polybutadiene polymers, maleinized polyisoprene polymers, maleinized polybutadiene/styrene polymers or mixtures thereof.
- Representative cross-linking agents include polyamine cross-linking agents.
- Representative surfactants include anionic and nonionic surfactants.
- Representative hydrophobic liquids include perfumes, insecticides, and insect repellants. In a preferred embodiment where the hydrophobic liquid is an insect repellant, the insect repellant is N,N-Diethyl-m-toluamide.
- the microemulsion additionally contains a water soluble additive.
- water soluble additives include water soluble colorants, water soluble dyes, water soluble pH color indicators, water soluble pigments, water soluble fragrances, and water soluble flavor materials.
- the gel composition is formed from a microemulsion that contains (a) from 1-70 wt. %, preferably from 1-40 wt. %, and more preferably from 10-25 wt. % of an anhydride functionalized polymer, (b) from 0.1-40 wt. %, preferably from 0.1-20 wt. %, and most preferably from 0.5-5 wt. % of a cross-linking agent, (c) from 0.01-50 wt. %, preferably from 0.1-20 wt. %, and more preferably from 0.5-10 wt. % surfactant, (d) from 0.01-30 wt. %, preferably from 0.1-10 wt.
- microemulsion is then gelled to form the clear, crosslinked, polymeric gel composition.
- the microemulsion is gelled in a mold and the resulting gel composition is then removed from the mold.
- the microemulsion is formed by combining a first premix containing the cross-linking agent and one or more of at least a portion of the hydrophobic liquid, the surfactant, and the water with a second premix containing the anhydride functionalized polymer and one or more of at least a portion of the hydrophobic liquid, the surfactant, and the water.
- the first premix contains the cross-linking agent, the surfactant, the water, and a first portion of the hydrophobic liquid.
- the second premix contains the anhydride functionalized composition, and a second portion of the hydrophobic liquid.
- the present invention provides a clear, crosslinked, polymeric gel made from a microemulsion that contains (a) from 1-70 wt. %, preferably from 1-40 wt. %, and more preferably from 10-25 wt. % of an anhydride functionalized polymer, (b) from 0.1-40 wt. %, preferably from 0.1-20 wt. %, and most preferably from 0.5-5 wt. % of a cross-linking agent, (c) from 0.01-50 wt. %, preferably from 0.1-20 wt. %, and more preferably from 0.5-10 wt. % surfactant, (d) from 0.01-30 wt. %, preferably from 0.1-10 wt.
- the combined proportion of (d) and (e) equals at least 30 wt. %, based on the total weight of the polymeric gel composition.
- the microemulsion contains from 1-70 wt. %, preferably from 1-40 wt. %, and more preferably from 10-25 wt. % of an anhydride functionalized polymer.
- Useful anhydride functionalized polymers are polymers made by reacting maleic anhydride with a suitable polymer, such as butadiene, isoprene, chloroisoprene, butadiene-styrene, other polyunsaturated hydrocarbons, including mixtures thereof, resulting in a covalent attachment of maleic anhydride to the polymer.
- suitable anhydride functionalized polymers include maleinized polybutadiene (such as Ricon 131MA10, available from Sartomer Co., Exton, Pa., and Lithene N4-9000-MA10, available from Synthomer Ltd., Essex, U.K.), maleinized polyisoprene (such as LIR-403, available from Kurary Co., Ltd., Tokyo, Japan), maleinized polybutadiene-styrene (such as Ricon 184), maleinized polychloroisoprene, maleinized polybutadiene-isoprene, and maleinized vegetable oil. Maleinized polybutadiene and maleinized polyisoprene are preferred. Maleinized polybutadiene is most preferred.
- the microemulsion also contains from 0.1-40 wt. %, preferably from 0.1-20 wt. %, and most preferably from 0.5-5 wt. % of a cross-linking agent for the anhydride functionalized polymer.
- the cross-linking agent can be a water soluble cross-linking agent.
- Representative water soluble cross-linking agents include polyoxyethylene diamine, such as Jeffamine D 2003.
- Suitable cross-linking agents are materials that react with an anhydride functionalized polymer to form a cross-linked polymer.
- the anhydride functionalized polymer and the cross-linking agent are included in a molar ratio of between about 3:1 and 0.5:1, preferably of about 1:1, based on the molar ratio of the functional groups which are present.
- cross-linking agents include, but are not limited to, compounds that contain an amine, alcohol, or thio functional group. Suitable cross-linking agents can also contain a combination of one or more thio, amine and alcohol functional groups. Also useful are the solid, heat-activated cross-linking agents disclosed in U.S. Pat. No. 5,844,047 (which patent is herein incorporated by reference).
- Preferred cross-linking agents include polythios, polyols, and polyamines, with polyamines being the most preferred cross-linking agent.
- Suitable polyamine cross-linking agents include (1) diamines, including polyoxypropylenediamine (such as Jeffamine D-400, available from Huntsman Corp., Salt Lake City, Utah) and triethyleneglycoldiamine (such as Jeffamine XTJ-504) and (2) triamines, including polyoxypropylenetriamine (such as Jeffamine T-403 and XTJ-509).
- Also useful are hindered polyamines, such as the hindered polyamines described in U.S. Pat. No. 5,633,341 (which patent is herein incorporated by reference) and polyamines contained within molecular sieves, such as the polyamines described in U.S. Pat. No. 5,792,816 (which patent is herein incorporated by reference).
- the microemulsion contains from 0.01-50 wt. %, preferably from 0.1-20 wt. %, and more preferably from 0.5-10 wt. % surfactant.
- Suitable surfactants include nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, cationic surfactants, anionic surfactants and combinations thereof.
- Preferred surfactants are nonionic and anionic surfactants.
- nonionic surfactants are ethoxylated nonylphenol containing 4 moles of ethylene oxide (such as Surfonic N40, available from Huntsman Corp., Salt Lake City, Utah) and ethoxylated alcohols containing 3 moles of ethylene oxide (such as Surfonic L243 and Tergitol 15-S-3, available from Dow Chemical Co., Midland, Mich.).
- anionic surfactants are ethoxylated alkyl sulfates (such as Steol CS460, available from Stephan Company, Northfield, Ill.).
- the microemulsion contains from 0.01-30 wt. %, preferably from 0.1-10 wt. %, and more preferably from 0.1-5 wt. % water and 10.0-95.0 wt. % hydrophobic liquid.
- the combined proportion of water and hydrophobic liquid equals at least 30 wt. %, based on the total weight of the polymeric gel composition.
- Suitable hydrophobic liquids that can be used in accordance with the invention include, but are not limited to, hydrocarbons, including oils, such as aliphatic 6: hydrocarbon oils and naphthenic hydrocarbon oils, such as paraffin oils, mineral oils, vegetable oils, and kerosene, fatty esters, fatty acids, triglycerides, diglycerides, monoglycerides, alcohols, including polypropylene glycol and propoxylated or ethoxylated alcohols, ethers, amides, polyamides, cyclic hydrocarbons, propoxylated or ethoxylated acids, propoxylated or ethoxlyated glycerides, silicon hydrocarbons, saturated or unsaturated synthetic oils, perfumes, hydrocarbon-containing fragrance raw materials, including those containing alcoholic, cyclic, aldehydic, ether, unstauration, sulfur, and keto functionalities, and essential oils, insecticides, and insect repellants.
- oils such as aliphatic 6:
- Useful insect repellants include any volatile insect repellant, such as pyrethroid insecticides, Citronella, citronellol, nerol, geraniol, and N,N-Diethyl-m-toluamide (DEET).
- a preferred insect repellant is DEET.
- One advantage of this invention is the ability of the microemulsion to incorporate water soluble additives and the compatibility of the water soluble additives in the resulting clear polymeric gel.
- water soluble additives that can be included in the microemulsion are pH color indicators, fluorescent dyes, water soluble dyes, and water soluble flavor and fragrance components. Specific examples include thymolphthalein and thymol blue pH color indicators.
- the present invention provides a method to produce the gel that comprises vigorously mixing (a) from 1-70 wt. %, preferably from 140 wt. %, and more preferably from 10-25 wt. % of an anhydride functionalized polymer, (b) from 0.1-40 wt. %, preferably from 0.1-20 wt. %, and most preferably from 0.5-5 wt. % of a cross-linking agent, (c) from 0.01-50 wt. %, preferably from 0.1-20 wt. %, and more preferably from 0.5-10 wt. % surfactant, (d) from 0.01-30 wt. %, preferably from 0.1-10 wt.
- the combined proportion of (d) and (e) equals at least 30 wt. %, based on the total weight of the polymeric gel composition.
- the microemulsion is characterized by the formation of water-in-oil micelles, that effectively minimize the diffraction of light in the visible wave-range.
- microemulsion then reacts at ambient temperature and pressure to gel and form a clear, cross-linked polymer gel.
- the microemulsion is placed in a mold where gelling occurs.
- the resulting structurally stable gel is then removed from the mold.
- the microemulsion is formed by first making two premixes, one containing the anhydride functionalized polymer and the other containing the cross-linking agent and then blending the premixes.
- the microemulsion is formed by combining a first premix containing the cross-linking agent and one or more of at least a portion of the hydrophobic liquid, the surfactant and the water with a second premix containing the cross-linking agent and one or more of at least a portion of the hydrophobic liquid, the surfactant and the water.
- the first premix contains the cross-linking agent, the surfactant, the water and all the hydrophobic liquid.
- the second premix contains the anhydride functionalized composition and all the hydrophobic liquid.
- aqueous gel was made using the following procedure.
- Premix A was made by combining 5.0 g of fragrance oil and 1.9 g of Lithene N4-9000-MA10 and mixed until homogeneous.
- Premix B was made by combining 2.4 g fragrance oil, 0.1 g water, 0.2 g Surfonic N40 and 0.3 g Jeffamine XTJ-403 and mixed until homogeneous.
- Premix A and Premix B were then combined and mixed vigorously for 15-30 seconds. This microemulsion was poured into a 2 inch diameter clear petri dish and the clarity was rated after the gel composition formed. The resulting gel was clear as seen in Table 1.
- aqueous gel was made using the procedure described in Example 1, except that Premix B contained 2.5 g fragrance oil and Jeffamine XTJ-509. The resulting gel was clear as seen in Table 1.
- aqueous gel was made using the procedure described in Example 1 except that Premix B contained 2.6 g fragrance oil and 0.2 g Surfonic L-24-3 and 0.2 g Jeffamine D-400. The resulting gel was clear as seen in Table 1.
- aqueous gel was made using the procedure described in Example 1 except that Premix B contained 2.6 g fragrance oil and 0.2 g Surfonic 15-S-3 and 0.2 g Jeffamine D-400. The resulting gel was clear as seen in Table l.
- Aqueous gels were formed using the procedure described in Example 1 except as follows.
- Premix A contained 5.0 g fragrance oil and 1.9 g Lithene.
- Premix B contained 2.4 g fragrance oil, 0.1 g water, 0.3 g Jeffamine T-403 and one of the following surfactants, (a) 0.2 g Surfonic N85, (b) 0.2 g Surfonic N120, of (c) a mix of 0.1 g Surfonic N40 and 0.1 g Surfonic N85. None of these gels were clear as seen in Table 1.
- aqueous gel composition was formed using the procedure described in Example 1, except that premix B did not contain a surfactant. The resulting gel composition was not clear as seen in Table 1.
- aqueous gel was made using the following procedure.
- Premix A was made by combining 10.0 g of fragrance oil and 3.8 g of Lithene N4-9000-MA10 and mixed until 11.1 homogeneous.
- Premix B was made by combining 5.0 g fragrance oil, 0.4 g water, 0.5 g. ethoxylated laural sodium sulfate, 0.1 g ethanol, 0.33 g Jeffamine D-400, and 0.1 g Jeffamine XTJ-509.
- Premix A and Premix B were then combined and mixed vigorously for 15-30 seconds. This microemulsion was poured into a 2 inch diameter clear petri dish and the clarity was rated after the gel composition formed. The resulting gel was clear as seen in Table 2.
- aqueous gel was made using the procedure described in Example 7, except that Premix B contained 5.5 6 g fragrance oil, 0.15 g water, 0.3 g ethoxylated laural sodium sulfate, and 0.05 g ethanol. The resulting gel was clear as seen in Table 2.
- aqueous gel was made using the procedure described in Example 7, except that Premix B contained 0.3 g water, 0.6 g ethoxylated laural sodium sulfate, and 0.1 g ethanol. The resulting gel was clear as seen in Table 2.
- aqueous gel was made using the procedure described in Example 7, except that Premix B contained 4.6 g fragrance oil, 0.3 g water, 0.6 g. ethoxylated laural sodium sulfate, and 0.4 g Jeffamine T-403. The resulting gel was clear as seen in Table 2.
- aqueous gel was made using the following procedure.
- Premix A was made by combining 10.0 g of fragrance oil and 3.8 g of Lithene N4-9000-MA10 and mixed until homogeneous.
- Premix B was made by combining 4.8 g fragrance oil, 0.3 g water, 0.3 g ethoxylated laural sodium sulfate, 0.1 g ethanol, 0.4 g Jeffamine D-400, and ca. 0.001 g LX1926 Pylachrome Purple.
- Premix A and Premix B were then combined and mixed vigorously for 15-30 seconds. This microemulsion was poured into a 2 inch diameter clear petri dish and the clarity was rated after the gel composition formed. The resulting gel composition was clear and the purple color was uniformly distributed throughout the gel.
- aqueous gel was made using the following procedure.
- Premix A was made by combining 5.0 g DEET and 1.9 g of Lithene N4-9000-MA10 and mixed until homogeneous.
- Premix B was made by combining 2.2 g fragrance oil, 0.15 g water, 0.05 g ethanol, 0.4 g Jeffamine T-3000. Premix A and Premix B were then combined and mixed vigorously for 15-30 seconds. This microemulsion was poured into a 2 inch diameter clear petri dish and the clarity was rated after the gel composition formed. The resulting gel composition was clear.
- aqueous gel was made using the procedure described in Example 12 except that Premix B contained 2.2 g of fragrance oil instead of DEET. The resulting gel was clear.
- aqueous gel composition was formed as described in U.S. Pat. No. 4,362,841.
- Microemulsion A was formed by combining 10 g fragrance oil, 10 g maleinized polyisoprene (LIR-403), 11.0 g Epicote 828, 0.5 g Ancamine K-54 and 1.5 g Surfonic L-24-3.
- aqueous gel composition was formed as described in U.S. Pat. No. 5,334,691. The following materials were combined as described in the patent: 74.8 g Carbowax 8000, 2.1 g Diethylene Glycol, 22.1 g Desmodur W, 1.0 g water, 0.2 g catalyst and 13.6 g urea. The resulting gel composition was not clear.
- inventive gel compositions are compatible with both hydrophobic liquids and water soluble materials and are aesthetically pleasing and functionally appropriate. It should be understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled the art and are to be included within the spirit and purview of this application and the scope of the appended claims.
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Abstract
Description
TABLE 1 | ||||||||||||
Exper- | Fra- | |||||||||||
iment | grance | Lithens | Surfonic | Surfonic | Surfonic | Surfonic | Tergitol | Jeffamine | Jeffamine | Jeffamine | Result | |
Number | Oil | N4-9000-MA10 | Water | N40 | N85 | N120 | L-24-3 | 15-S-3 | T-403 | XTJ-509 | D-400 | (1) |
1 | 7.4 | 1.9 | 0.1 | 0.2 | — | — | — | — | 0.3 | — | — | Clear |
2 | 7.5 | 1.9 | 0.1 | 0.2 | — | — | — | — | — | 0.3 | — | Clear |
3 | 7.6 | 1.9 | 0.1 | — | — | — | 0.2 | — | — | — | 0.2 | Clear |
4 | 7.6 | 1.9 | 0.1 | — | — | — | — | 0.2 | — | — | 0.2 | Clear |
5 | 7.4 | 1.9 | 0.1 | — | 0.2 | — | — | — | 0.3 | — | — | Hazy |
6 | 7.4 | 1.9 | 0.1 | — | — | — | — | — | 0.3 | — | — | Cloudy |
(1) The clarity of each gel composition was judged on a scale ranging from clear, hazy, cloudy, and opaque. |
TABLE 2 | ||||||||||||
Lithene | TEA | Laural | Alkyl | Ethoxylated | ||||||||
Experiment | Fragrance | N4-9000 | Laural | Sulfate | Sulfonate | Laural | Jeffamine | Jeffamine | Jeffamine | |||
Number | Oil | MA10 | Water | Sulfate | NH3 salt | Na salt | Na Sulfate | Ethanol | D-400 | XTJ-509 | T-403 | Result (1) |
7 | 15.0 | 3.8 | 0.4 | — | — | — | 0.5 | 0.1 | 0.33 | 0.1 | — | Clear |
8 | 15.5 | 3.8 | 0.15 | — | — | — | 0.3 | 0.05 | 0.33 | 0.1 | — | Clear |
9 | 15 | 3.8 | 0.3 | — | — | — | 0.6 | 0.1 | 0.33 | 0.1 | — | Clear |
10 | 14.6 | 3.8 | 0.3 | — | — | — | 0.6 | 0.1 | — | — | 0.4 | Clear |
(1) The clarity of each gel composition was judged on a scale ranging from clear, hazy, cloudy, and opaque. |
Claims (12)
Priority Applications (5)
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US10/040,412 US6846491B1 (en) | 2001-08-28 | 2002-01-07 | Clear, polymeric gel composition and method for producing the same |
MXPA04001941A MXPA04001941A (en) | 2001-08-28 | 2002-08-26 | Clear, polymeric gel composition and method for producing the same. |
EP02757383A EP1458470A1 (en) | 2001-08-28 | 2002-08-26 | Clear, polymeric gel composition and method for producing the same |
CA002458910A CA2458910C (en) | 2001-08-28 | 2002-08-26 | Clear, polymeric gel composition and method for producing the same |
PCT/US2002/027108 WO2003020412A1 (en) | 2001-08-28 | 2002-08-26 | Clear, polymeric gel composition and method for producing the same |
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US31540201P | 2001-08-28 | 2001-08-28 | |
US10/040,412 US6846491B1 (en) | 2001-08-28 | 2002-01-07 | Clear, polymeric gel composition and method for producing the same |
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EP (1) | EP1458470A1 (en) |
CA (1) | CA2458910C (en) |
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WO (1) | WO2003020412A1 (en) |
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US20070128931A1 (en) * | 2005-12-05 | 2007-06-07 | Ziwei Liu | Polyester gel adapted for use with polycarbonate components |
US20080015295A1 (en) * | 2006-07-11 | 2008-01-17 | Williams Virgil Ag | Polymeric gel composition and method for making |
US20080070025A1 (en) * | 2004-05-27 | 2008-03-20 | Pavlin Mark S | Compositions and articles containing a cross-linked polymer matrix and an immobilized active liquid, as well as methods of making and using the same |
US20080207049A1 (en) * | 2007-02-28 | 2008-08-28 | Ziwei Liu | Nanocone silicone gel for telecommunication interconnect devices |
US20090149566A1 (en) * | 2007-12-06 | 2009-06-11 | Sven Dobler | Fragrant gel polymer system |
US20110117156A1 (en) * | 2004-05-27 | 2011-05-19 | Arizona Chemical Company | Compositions and articles containing an active liquid in a polymeric matrix and methods of making and using the same |
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US9850449B2 (en) | 2010-07-08 | 2017-12-26 | Orlandi, Inc. | Fragrant gel polymer with solvents |
CN109200953A (en) * | 2018-07-25 | 2019-01-15 | 华南理工大学 | A kind of cellulose base hydrogel microsphere and its preparation method and application |
WO2021160670A1 (en) | 2020-02-13 | 2021-08-19 | Glycoscience, S.L. | 3'-ketoglycoside compound for the slow release of a volatile alcohol |
WO2023099327A1 (en) | 2021-11-30 | 2023-06-08 | Glycoscience, S.L. | Slow-release formulation |
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DE10253255A1 (en) * | 2002-11-15 | 2004-06-03 | Air & D - Sarl | Pesticide Formulation |
ES2626151T3 (en) | 2010-03-12 | 2017-07-24 | Monsanto Technology Llc | Agrochemical gel compositions |
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- 2002-01-07 US US10/040,412 patent/US6846491B1/en not_active Expired - Lifetime
- 2002-08-26 EP EP02757383A patent/EP1458470A1/en not_active Withdrawn
- 2002-08-26 MX MXPA04001941A patent/MXPA04001941A/en active IP Right Grant
- 2002-08-26 WO PCT/US2002/027108 patent/WO2003020412A1/en not_active Application Discontinuation
- 2002-08-26 CA CA002458910A patent/CA2458910C/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
WO2003020412A1 (en) | 2003-03-13 |
CA2458910A1 (en) | 2003-03-13 |
MXPA04001941A (en) | 2005-09-08 |
EP1458470A1 (en) | 2004-09-22 |
CA2458910C (en) | 2008-01-15 |
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